TWI687498B - Adhesive resin layer and adhesive resin film - Google Patents

Adhesive resin layer and adhesive resin film Download PDF

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Publication number
TWI687498B
TWI687498B TW105105824A TW105105824A TWI687498B TW I687498 B TWI687498 B TW I687498B TW 105105824 A TW105105824 A TW 105105824A TW 105105824 A TW105105824 A TW 105105824A TW I687498 B TWI687498 B TW I687498B
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adhesive resin
resin layer
adhesive
layer
temperature
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TW105105824A
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Chinese (zh)
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TW201641648A (en
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藤田志朗
鈴木淳史
新見洋人
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日商藤森工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

In the present invention, an adhesion resin layer and an adhesion resin film is provided. The adhesion resin layer may prevent the formation of bubbles even when it is adhered to a substrate with a high height difference. In addition, a stacking layer which is stacked in an order of a substrate, the adhesion layer, and a substrate may have good durability since the stacking layer may endure heating and humidity without forming bubbles, and the transparency of the stacking layer can still be maintained. More specifically, the present invention is related to a monolayer of an adhesion resin layer, which includes an acrylic-base adhesion resin composition with transparency. The adhesion resin composition includes (A) acrylic polymer, (B) urethane acrylate, and (C) thermal polymerization initiator and may optionally includes acrylic monomer. Two surfaces of the adhesion layer 11 are adhesive under normal temperature, and the adhesion layer 11 can be thermalsetted by heating at a temperature of 100 to 250℃ for 30 seconds to 10 minutes.

Description

接著性樹脂層以及接著性樹脂薄膜 Adhesive resin layer and adhesive resin film

本發明，係有關於一種即便貼合在具有段差的基材亦能夠防止產生氣泡之接著性樹脂層及接著性樹脂薄膜。 The present invention relates to an adhesive resin layer and an adhesive resin film that can prevent the generation of air bubbles even when bonded to a substrate having a step.

本申請案，係基於2015年5月18日提出申請之日本國特願2015-100644號而主張優先權，而且將其內容引用在此。 This application claims priority based on Japanese Patent Application No. 2015-100644 filed on May 18, 2015, and the contents are cited here.

作為使用後能夠容易地將黏著劑剝離之黏著劑，係使用含有丙烯酸系黏著劑、胺甲酸酯丙烯酸酯等的光硬化型丙烯酸酯化合物、異氰酸酯系硬化劑(交聯劑)、及光聚合起始劑之黏著劑(例如，參照專利文獻1~3)。此種黏著劑係在常溫具有黏著性之同時，因為藉由光照射而使黏著性降低而能夠再剝離，所以被廣泛地使用在半導體加工用或搬運用黏著膠帶。 As an adhesive that can easily peel off the adhesive after use, a photo-curable acrylate compound containing an acrylic adhesive, urethane acrylate, etc., an isocyanate-based hardener (crosslinking agent), and photopolymerization are used The adhesive of the initiator (for example, refer to Patent Documents 1 to 3). This type of adhesive has adhesiveness at room temperature, and it can be peeled off by reducing the adhesiveness by light irradiation, so it is widely used as an adhesive tape for semiconductor processing or transportation.

另一方面，因為丙烯酸系黏著劑，亦能夠與觸控面板、行動電話、顯示器、貼合玻璃等具有透明性或透光性的基材積層而接著，所以被廣泛地使用。基材表面係有因印刷層、配線、電極、框體等而具有段差之情形。將黏著劑積層在具有段差的基材時，在段差與黏著劑之間產生空隙且殘留氣泡時，基材間的接著強度及通過基材後的光學特性有低落之可能性。 On the other hand, acrylic adhesives can also be laminated with transparent or translucent substrates such as touch panels, mobile phones, displays, and laminated glass, and are therefore widely used. The surface of the base material may have a step difference due to the printed layer, wiring, electrode, frame, etc. When the adhesive is laminated on a substrate having a step, when a gap is generated between the step and the adhesive and bubbles remain, the adhesive strength between the substrates and the optical characteristics after passing through the substrate may be reduced.

先前技術文獻 Prior technical literature 專利文獻 Patent Literature

[專利文獻1]日本特許第3764133號公報 [Patent Document 1] Japanese Patent No. 3764133

[專利文獻2]日本特許第3803200號公報 [Patent Document 2] Japanese Patent No. 3803200

[專利文獻3]日本特開2012-193321號公報 [Patent Document 3] Japanese Unexamined Patent Publication No. 2012-193321

本發明係鑒於上述情形而進行，其課題係提供一種接著性樹脂層及接著性樹脂薄膜，其係即便是與具有較高的段差之基材貼合，亦能夠防止產生氣泡；依照以下的順序將基材、接著性樹脂層、及基材積層而成之積層體，在耐熱後及耐濕熱後不產生氣泡，而且耐久性良好且能夠維持透明性。 The present invention has been carried out in view of the above circumstances, and its object is to provide an adhesive resin layer and an adhesive resin film, which can prevent the generation of air bubbles even if it is bonded to a substrate having a high step difference; in the following order The laminate formed by laminating the base material, the adhesive resin layer, and the base material does not generate bubbles after heat resistance and humidity resistance, and has good durability and can maintain transparency.

為了解決前述課題，本發明係提供一種接著性樹脂層，其係含有具有透明性的丙烯酸系接著性樹脂組成物之單層的接著性樹脂層，其特徵在於：前述接著性樹脂組成物最少含有(A)丙烯酸系聚合物、(B)胺甲酸酯丙烯酸酯(Urethane acrylate)、及(C)熱聚合起始劑，前述接著性樹脂層係於常溫在兩面具有黏著性，能夠藉由於100~250℃的溫度及加熱30秒~10分鐘的時間而熱硬化。 In order to solve the aforementioned problems, the present invention provides an adhesive resin layer comprising a single-layer adhesive resin layer of a transparent acrylic adhesive resin composition, characterized in that the adhesive resin composition contains at least (A) Acrylic polymer, (B) Urethane acrylate, and (C) Thermal polymerization initiator. The adhesive resin layer has adhesiveness on both sides at normal temperature. Heat curing at a temperature of ~250°C and heating for 30 seconds to 10 minutes.

相對於前述(A)丙烯酸系聚合物100重量份，前述(B)胺甲酸酯丙烯酸酯的添加量係以2~50重量份為佳。 The added amount of the (B) urethane acrylate is preferably 2 to 50 parts by weight relative to 100 parts by weight of the (A) acrylic polymer.

前述熱聚合起始劑，係以過氧化物為佳。 The aforementioned thermal polymerization initiator is preferably a peroxide.

前述過氧化物，係以具有1分鐘的半衰期之溫度為100℃以上為佳。 The aforementioned peroxide is preferably a temperature having a half-life of 1 minute of 100°C or higher.

前述(A)丙烯酸系聚合物，係以藉由硬化劑交聯而成之丙烯酸系聚合物為佳。 The aforementioned (A) acrylic polymer is preferably an acrylic polymer cross-linked by a hardener.

前述硬化劑，係以含有異氰酸酯系化合物或環氧系化合物的至少1種類為佳。 The hardener is preferably at least one kind containing an isocyanate compound or an epoxy compound.

前述接著性樹脂組成物，係能夠含有前述(B)胺甲酸酯丙烯酸酯以外的(D)丙烯酸系單體。 The adhesive resin composition may contain (D) acrylic monomers other than the (B) urethane acrylate.

又，本發明係提供一種接著性樹脂薄膜，其特徵在於：在2片隔離膜之間，積層前述接著性樹脂層而成。 Furthermore, the present invention provides an adhesive resin film, characterized in that the adhesive resin layer is laminated between two separators.

而且，本發明係提供一種積層體，其特徵在於：透過前述接著性樹脂層而積層2片基材而成。 Furthermore, the present invention provides a laminate characterized by laminating two substrates through the adhesive resin layer.

又，本發明係提供一種積層體之製造方法，其特徵在於：透過前述接著性樹脂層而積層2片基材，在將所得到的積層體夾在2個模具之間之狀態下，將前述接著性樹脂層進行加熱硬化。 In addition, the present invention provides a method for manufacturing a laminated body, characterized in that two substrates are laminated through the adhesive resin layer, and the obtained laminated body is sandwiched between two molds. The subsequent resin layer is heat-cured.

將在前述接著性樹脂層的原材料組成物所含有的溶劑之沸點設為溫度A，將前述熱聚合起始劑具有半衰期在1分鐘之溫度設為溫度B，將在前述接著性樹脂層之製造步驟中用以將前述溶劑除去之加熱時的溫度設為溫度C，將在使前述接著性樹脂層加熱硬化之步驟之模具的加壓溫度設為溫度D時，各溫度係以下述式(1)的順序為佳。 The boiling point of the solvent contained in the raw material composition of the adhesive resin layer is set to temperature A, and the temperature at which the thermal polymerization initiator has a half-life of 1 minute is set to temperature B. In the step, the temperature at which the solvent is removed during heating is set to temperature C, and when the pressing temperature of the mold in the step of heating and curing the adhesive resin layer is set to temperature D, each temperature is represented by the following formula (1 ) Is better.

式(1) 溫度A<溫度C<溫度B<溫度D Formula (1) Temperature A<Temperature C<Temperature B<Temperature D

前述2片基材之至少一方的基材，係在與前述接 著性樹脂層接觸側之面內，能夠含有1個以上之5μm~1mm的段差。 The base material of at least one of the two base materials is included in the surface on the side in contact with the adhesive resin layer, and can contain one or more steps of 5 μm to 1 mm.

前述段差係以50μm~1mm為佳。 The aforementioned step difference is preferably 50 μm to 1 mm.

本發明的接著性樹脂層，其厚度係以比段差更厚為佳。本發明的接著性樹脂層之厚度係段差的1.1~3倍，例如以5.5μm~3mm為佳，以55μm~3mm為較佳，更佳是段差的厚度之1.2~2倍，例如以6μm~2mm為佳，以60μm~2mm為較佳。 The thickness of the adhesive resin layer of the present invention is preferably thicker than the step. The thickness of the adhesive resin layer of the present invention is 1.1 to 3 times the step difference, for example, 5.5 μ m to 3 mm is better, 55 μ m to 3 mm is more preferable, and 1.2 to 2 times the thickness of the step difference is more preferable, for example 6 μm ~2mm is better, and 60 μm ~2mm is better.

前述加熱硬化時之模具溫度，係以150~300℃的溫度為佳。 The temperature of the mold during the heating and curing is preferably 150 to 300°C.

本發明之特徵在於：含有丙烯酸系聚合物、胺甲酸酯丙烯酸酯、及熱聚合起始劑，藉由前述成分能夠製造轉移膠帶狀(Transfer tape-like)接著性樹脂層。接著性樹脂層係藉由胺甲酸酯丙烯酸酯而對具有段差的基材具有基材追隨性。能夠提供一種接著性樹脂層以及其製造方法，該接著性樹脂層係藉由熱等的反應開始條件而硬化胺甲酸酯丙烯酸酯，即便有段差，氣泡亦不進入。特別是藉由在胺甲酸酯丙烯酸酯的添加量下工夫，能夠保持對基材的追隨性、及轉移膠帶狀接著性樹脂層本身的強度。依照本發明，藉由強迫地、特別是熱壓而能夠使接著性樹脂層半強迫地追隨基材。從在積層體製造時不是藉由透過空氣之電子射線照射或能量線照射引起硬化，而是不透過空氣之熱及壓力的雙方對積層體施加熱壓，從抑制產生氣泡及耐久性的觀點而言，乃是較佳。 The present invention is characterized by containing an acrylic polymer, a urethane acrylate, and a thermal polymerization initiator, and a transfer tape-like adhesive resin layer can be produced with the aforementioned components. The adhesive resin layer has base material followability to the base material having a step by urethane acrylate. It is possible to provide an adhesive resin layer and a method for manufacturing the adhesive resin layer. The adhesive resin layer hardens the urethane acrylate by reaction start conditions such as heat, and even if there is a step, bubbles do not enter. In particular, by taking care of the amount of urethane acrylate added, it is possible to maintain the followability to the base material and the strength of the transfer tape-like adhesive resin layer itself. According to the present invention, the adhesive resin layer can be semi-forced to follow the base material by forced, particularly hot pressing. From the point of view of suppressing the generation of bubbles and durability, the laminate is not hardened by electron beam irradiation or energy beam irradiation through the air during the manufacture of the laminate, but the heat and pressure of the air are not applied to the laminate. Words are better.

依照本發明，能夠提供一種接著性樹脂層及接著性樹脂薄膜，其中該接著性樹脂層係即便與具有較高的段差之 基材貼合，亦能夠防止產生氣泡且能夠維持透明性。 According to the present invention, it is possible to provide an adhesive resin layer and an adhesive resin film, wherein the adhesive resin layer has a higher level difference The bonding of the substrate can also prevent the generation of bubbles and maintain transparency.

10‧‧‧接著性樹脂薄膜 10‧‧‧adhesive resin film

11‧‧‧接著性樹脂層 11‧‧‧adhesive resin layer

11a、11b‧‧‧接著性樹脂層的兩面(黏著面) 11a, 11b‧‧‧Two sides of adhesive resin layer (adhesive surface)

12、13‧‧‧隔離膜 12, 13‧‧‧ isolation film

12a、13a‧‧‧隔離膜表面(剝離面) 12a, 13a‧‧‧Isolation membrane surface (peeling surface)

20、30‧‧‧積層體 20, 30‧‧‧Layered body

21、22‧‧‧基材 21, 22‧‧‧ substrate

21a、22a‧‧‧內表面 21a, 22a‧‧‧Inner surface

21b、22b‧‧‧外表面 21b, 22b‧‧‧External surface

23‧‧‧凸部 23‧‧‧Convex

24‧‧‧段差的角落部 24‧‧‧ Corner

25‧‧‧熱硬化後的接著層 25‧‧‧The layer after heat hardening

31、32‧‧‧模具 31, 32‧‧‧ mold

31a、32a‧‧‧按壓面 31a, 32a‧‧‧Pressing surface

第1圖係顯示發明的接著性樹脂薄膜的一個例子之剖面圖。 Fig. 1 is a cross-sectional view showing an example of the adhesive resin film of the invention.

第2圖係顯示具有段差的基材的一個例子之剖面圖。 Fig. 2 is a cross-sectional view showing an example of a substrate having a step.

第3圖係顯示2片基材之間積層有接著性樹脂層之積層體的一個例子之剖面圖。 FIG. 3 is a cross-sectional view showing an example of a laminate in which an adhesive resin layer is laminated between two substrates.

第4圖係顯示將第3圖的積層體夾在模具之間之狀態的一個例子之剖面圖。 FIG. 4 is a cross-sectional view showing an example of a state in which the laminate of FIG. 3 is sandwiched between molds.

第5圖係顯示將接著性樹脂層加熱硬化後之積層體的一個例子之剖面圖。 FIG. 5 is a cross-sectional view showing an example of a laminate after heat-hardening the adhesive resin layer.

用以實施發明之形態 Forms for carrying out the invention

以下，係基於較佳實施形態，參照圖式而說明本發明。 Hereinafter, the present invention will be described based on the preferred embodiments with reference to the drawings.

在第1圖，係顯示接著性樹脂薄膜10的一個例子之剖面圖。接著性樹脂薄膜10係具有：2片隔離膜12、13；及被積層在該等之間之接著性樹脂層11。構成接著性樹脂層11之接著性樹脂組成物，係含有(A)丙烯酸系聚合物、(B)胺甲酸酯丙烯酸酯、及(C)熱聚合起始劑。接著性樹脂層11的兩面11a、11b係在常溫具有黏著性(成為黏著面)。 Fig. 1 is a cross-sectional view showing an example of the adhesive resin film 10. The adhesive resin film 10 includes: two separators 12 and 13; and an adhesive resin layer 11 laminated between these. The adhesive resin composition constituting the adhesive resin layer 11 contains (A) an acrylic polymer, (B) a urethane acrylate, and (C) a thermal polymerization initiator. Both surfaces 11a and 11b of the adhesive resin layer 11 have adhesiveness at room temperature (become an adhesive surface).

又，在本說明書中，所謂「常溫」係約3℃~約40℃，以約10℃~約30℃為佳，較佳為約15℃~約25℃，最佳為是約 23℃。 In this specification, the "normal temperature" is about 3°C to about 40°C, preferably about 10°C to about 30°C, preferably about 15°C to about 25°C, and most preferably about 23℃.

接著性樹脂層11係在遍及厚度方向的全體含有接著性樹脂組成物。只要含有滿足必要條件之接著性樹脂組成物，接著性樹脂層11亦可由含有同種或異種接著性樹脂組成物之2層以上所構成。接著性樹脂層11係由單層的接著性樹脂層所構成時，因為能夠使層構成單純化而減低成本，乃是較佳。接著性樹脂組成物係含有丙烯酸系接著性樹脂(聚合物)且具有透明性。 The adhesive resin layer 11 contains the adhesive resin composition throughout the thickness direction. As long as the adhesive resin composition satisfying the necessary conditions is contained, the adhesive resin layer 11 may be composed of two or more layers containing the same or different adhesive resin composition. When the adhesive resin layer 11 is composed of a single adhesive resin layer, it is preferable because the layer structure can be simplified and the cost can be reduced. The adhesive resin composition contains an acrylic adhesive resin (polymer) and has transparency.

隔離膜12、13，係在接著性樹脂層11接觸側的表面12a、13a，具有剝離性(成為剝離面)。作為隔離膜12、13之構成，可舉出在樹脂薄膜的一面或兩面設置有剝離劑層之構成、及在樹脂薄膜的樹脂內含有剝離劑之構成。亦能夠使用紙、合成紙、金屬箔、各種薄片等代替樹脂薄膜。隔離膜12、13係具有透明性時，因為能夠在不將隔離膜12、13剝離之接著性樹脂薄膜10的狀態下，進行接著性樹脂層11的光學檢査，乃是較佳。 The separators 12, 13 are on the surfaces 12a, 13a on the contact side of the adhesive resin layer 11, and have peelability (being a peeling surface). Examples of the configuration of the separators 12 and 13 include a configuration in which a release agent layer is provided on one or both surfaces of the resin film, and a configuration in which a release agent is contained in the resin of the resin film. Paper, synthetic paper, metal foil, various sheets, etc. can also be used instead of the resin film. When the separators 12 and 13 have transparency, it is preferable that the adhesive resin layer 11 can be optically inspected without peeling off the adhesive resin film 10 of the separators 12 and 13.

第1圖所顯示的接著性樹脂薄膜10，係能夠藉由將隔離膜12、13從接著性樹脂層11剝離而露出的黏著面11a、11b，貼合2片基材。在第3圖，係顯示在2片基材21、22之間積層有接著性樹脂層11之積層體20的一個例子。2片基材21、22之中至少一方(在此為基材21)係如第2圖所顯示，具有凸部23所產生的段差。凸部23所產生的段差，係可存在於2片基材21、22與接著性樹脂層11接觸側之面21a、22a的一方，亦可存在於雙方。 The adhesive resin film 10 shown in FIG. 1 can be bonded to two substrates by the adhesive surfaces 11 a and 11 b exposed by peeling the separators 12 and 13 from the adhesive resin layer 11. FIG. 3 shows an example of the laminate 20 in which the adhesive resin layer 11 is laminated between the two base materials 21 and 22. At least one of the two substrates 21 and 22 (here, the substrate 21) has a step caused by the convex portion 23 as shown in FIG. 2. The step caused by the convex portion 23 may exist on one of the surfaces 21a, 22a on the side where the two base materials 21, 22 are in contact with the adhesive resin layer 11, or may exist on both sides.

在第2圖中，雖然凸部23與基材21係分別顯示，但是凸部23亦可與基材21為一體。例如，在基材的表面形成有凹凸時，從凹部的底部起至凸部的頂部之間(高低差)係成為段差。在與接著性樹脂層11接觸側之面21a、22a所設置的段差，可為大小混合，亦可包含5μm~1mm、較佳為50μm~1mm的段差。 In FIG. 2, although the convex portion 23 and the base material 21 are shown separately, the convex portion 23 may be integrated with the base material 21. For example, when irregularities are formed on the surface of the base material, the level (height difference) from the bottom of the concave portion to the top of the convex portion becomes a level difference. The step provided on the surfaces 21a, 22a on the side in contact with the adhesive resin layer 11 may be a mixed size, and may include a step of 5 μm to 1 mm, preferably 50 μm to 1 mm.

基材21、22係被接著性樹脂層11貼合之被接著物。各基材21、22可以是硬質板，亦可以是如薄膜具有可撓性。例如可以是玻璃、聚碳酸酯、丙烯酸樹脂、各種樹脂、陶瓷、金屬等的單板，亦可以是液晶面板、觸控面板、玻璃蓋片、配線基板等由複數種材料所構成之複合體。基材21、22的外表面21b、22b係可為平坦，亦可具有凹凸。 The base materials 21 and 22 are adherends bonded by the adhesive resin layer 11. Each of the base materials 21 and 22 may be a rigid board, or may have flexibility such as a thin film. For example, it may be a single board of glass, polycarbonate, acrylic resin, various resins, ceramics, metal, etc., or it may be a composite body composed of a plurality of materials such as a liquid crystal panel, a touch panel, a glass cover sheet, a wiring board, and the like. The outer surfaces 21b and 22b of the base materials 21 and 22 may be flat or may have irregularities.

形成如第3圖的積層體20時，將隔離膜12、13剝離之順序係沒有特別限定。可以在將一方的隔離膜剝離而露出之一方的黏著面，貼合一方的基材之後，將另一方的隔離膜剝離而在露出之另一方的黏著面，貼合另一方的基材。亦可將雙方的隔離膜剝離而露出雙方的黏著面之後，貼合各自的基材。 When forming the layered body 20 as shown in FIG. 3, the order in which the separation films 12 and 13 are peeled off is not particularly limited. After one of the separators is peeled to expose one of the adhesive surfaces and one of the substrates is bonded, the other separator may be peeled to stick the other substrate to the exposed adhesive surface. It is also possible to peel off the separators of both sides to expose the adhesive surfaces of both sides, and then adhere to the respective substrates.

因為接著性樹脂層11係含有具有流動性之(B)胺甲酸酯丙烯酸酯，所以柔軟性較高，而能夠藉由接著性樹脂組成物使至凸部23的段差之角落部24為止濕潤化。因此，即便段差較大，亦能夠抑制產生氣泡。因為接著性樹脂層11係含有(C)熱聚合起始劑，所以可藉由貼合後使其熱硬化，而使接合更堅固。相較於照射紫外光，熱硬化的設備係具有較簡便， 即便基材係包含透光性較低的部分時亦能夠確實地硬化之優點。 Since the adhesive resin layer 11 contains (B) urethane acrylate having fluidity, it has high flexibility and can be wetted by the adhesive resin composition up to the corner portion 24 of the step of the convex portion 23 Change. Therefore, even if the step difference is large, the generation of bubbles can be suppressed. Since the adhesive resin layer 11 contains (C) a thermal polymerization initiator, it is possible to make the bonding stronger by thermally curing it after bonding. Compared with irradiating ultraviolet light, heat-hardening equipment is more convenient, Even if the base material includes a portion with low light transmittance, it can be hardened reliably.

透過接著性樹脂層11而將2片基材21、22積層而得到的積層體20，係如第4圖所顯示，藉由夾在2個模具31、32之間的狀態下進行加熱，能夠使接著性樹脂層11硬化。藉此，(A)丙烯酸系聚合物及(B)胺甲酸酯丙烯酸酯進行反應(聚合、交聯等)，使得基材21、22之間的接著力上升。又，藉由加熱之同時進行加壓，即便在段差的周邊殘留有氣泡，填埋空隙而能夠將氣泡除去。進行加熱硬化時、係加熱模具31、32的至少一方。 The laminate 20 obtained by laminating two base materials 21 and 22 through the adhesive resin layer 11 can be heated by being sandwiched between two molds 31 and 32 as shown in FIG. 4. The adhesive resin layer 11 is hardened. As a result, (A) the acrylic polymer and (B) the urethane acrylate react (polymerization, cross-linking, etc.), so that the adhesion between the substrates 21 and 22 increases. In addition, by applying pressure while heating, even if air bubbles remain around the step, the air gaps can be filled to remove the air bubbles. At the time of heat curing, at least one of the molds 31 and 32 is heated.

將積層體20熱壓時，在模具31、32與積層體20之間(詳言之，在模具31、32的按壓面31a、32a與基材21、22的外表面21b、22b之間)，亦可使緩衝片、剝離片、保護片等(夾雜物)介於中間。在基材21、22的外表面21b、22b具有凹凸時，因為外表面的凸部直接接觸模具31、32時，壓力容易集中在凸部，所以設置上述的夾雜物為佳。 When the laminate 20 is hot pressed, between the molds 31, 32 and the laminate 20 (specifically, between the pressing surfaces 31a, 32a of the molds 31, 32 and the outer surfaces 21b, 22b of the base materials 21, 22) Also, the buffer sheet, peeling sheet, protective sheet, etc. (inclusions) can be interposed. When the outer surfaces 21b and 22b of the base materials 21 and 22 have irregularities, since the convex portions of the outer surface directly contact the molds 31 and 32, the pressure tends to concentrate on the convex portions, so it is preferable to provide the above-mentioned inclusions.

在第4圖，模具31、32係不將積層體20的側面覆蓋，但是亦可以是在模具31、32的一方或雙方設置有凹凸，而以積層體20的側面為被模具覆蓋之方式構成。例如亦可以是將一方的模具設作凸型，將另一方的模具設作凹型，將積層體20收容在凹型的凹部以後，使凸型的凸部朝向凹型的凹部接近。 In FIG. 4, the molds 31 and 32 do not cover the side surfaces of the laminate 20, but one or both of the molds 31 and 32 may be provided with concavities and convexities, and the side surfaces of the laminate 20 may be configured to be covered by the mold . For example, one mold may be convex, and the other mold may be concave. After the laminate 20 is accommodated in the concave recess, the convex convex portion may approach the concave concave portion.

在第5圖，係顯示藉由加熱硬化而得到積層體30的一個例子。在該積層體30，作為接著性樹脂層11熱硬化後 之結果，係在2片基材21、22之間，積層含有熱硬化後的接著性樹脂之接著層25。因為熱硬化後的接著層25係硬度増大，所以即便加熱前的接著性樹脂層11為柔軟亦不容易再剝離。藉此，作為接著性樹脂層11，係能夠使用即便接著力較低但是段差追隨性優異的樹脂。 FIG. 5 shows an example of the laminate 30 obtained by heat curing. After the laminated body 30 is thermally cured as the adhesive resin layer 11, As a result, the adhesive layer 25 containing the adhesive resin after thermosetting is laminated between the two substrates 21 and 22. Since the hardness of the adhesive layer 25 after heat curing is increased, it is not easy to peel off even if the adhesive resin layer 11 before heating is soft. As a result, as the adhesive resin layer 11, even if the adhesive force is low, it is possible to use a resin excellent in step followability.

在製造積層體30時，例如基材21具有凹凸，而基材22為平坦時，能夠考慮若干種製造方法。積層體30的製造係能夠採用任一種方法。 When manufacturing the laminate 30, for example, when the base material 21 has irregularities and the base material 22 is flat, several manufacturing methods can be considered. Either method can be used for the manufacturing system of the laminate 30.

作為第1積層方法，可舉出在具有凹凸之基材21積層接著性樹脂層11，隨後，實施高壓釜處理，在接著性樹脂層11上積層平坦的基材22且積層積層體20之後，或是邊層積基材22邊使用模具31、32而使接著性樹脂層11加熱硬化之方法。 As a first lamination method, an adhesive resin layer 11 is laminated on a substrate 21 having irregularities, and then, an autoclave treatment is performed, after a flat substrate 22 is laminated on the adhesive resin layer 11 and a laminate 20 is laminated, Or a method of heating and curing the adhesive resin layer 11 using the molds 31 and 32 while laminating the base material 22.

作為第2積層方法，可舉出在平坦的基材22積層接著性樹脂層11，隨後，實施高壓釜處理，在接著性樹脂層11上積層具有凹凸之基材21之後，或是邊層積基材21邊使用模具31、32而使接著性樹脂層11加熱硬化之方法。 As the second lamination method, the adhesive resin layer 11 is laminated on a flat base material 22, and then an autoclave treatment is performed, after the base material 21 having irregularities is laminated on the adhesive resin layer 11, or the edge is laminated A method of heating and curing the adhesive resin layer 11 using the molds 31 and 32 while using the base material 21.

作為第3積層方法，可舉出將具有凹凸之基材21、接著性樹脂層11、平坦的基材22同時積層之後，或是在積層之同時，使用模具31、32使接著性樹脂層11加熱硬化之方法。 As the third lamination method, after the substrate 21 having the unevenness, the adhesive resin layer 11 and the flat substrate 22 are simultaneously laminated, or at the same time, the adhesive resin layer 11 is made using the molds 31 and 32 Heat hardening method.

第1積層方法，藉由將具有凹凸之基材21與接著性樹脂層11先貼合而進行高壓釜處理，因為接著性樹脂層變得容易追隨凹凸，所以是即便熱壓加工的條件為較大的偏差氣泡亦能夠較少之方法。又，就能夠縮短製程而言，第3積層方 法係在成本面最具有優點之方法。 In the first lamination method, the substrate 21 having the unevenness and the adhesive resin layer 11 are bonded together to perform the autoclave process. Since the adhesive resin layer becomes easy to follow the unevenness, the conditions of the hot pressing process are Large deviation bubbles can also be reduced. Also, in terms of being able to shorten the process, the third The law system has the most advantages in terms of cost.

在第2圖~第5圖，基材21、22的段差，係預先在熱壓前設置在基材，但是亦可以在基材21、22間積層接著性樹脂層11而熱壓時，使基材21、22的一方或雙方變形而產生段差。例如在模具31、32的按壓面31a、32a設置凹凸時，能夠使樹脂薄膜等具有可撓性之基材21、22變形。藉由最初接著性樹脂層11具有流動性，而能夠追隨基材21、22的段差。又，藉由熱壓之間進行熱聚合，接著性樹脂層11硬化而能夠抑制產生空隙及氣泡。而且，藉由基材21、22係與接著層25接合，基材的變形被固定而能夠實現凹凸的成形。在基材的內表面形成有凸部時，亦可在背側的外表面形成有凹部。 In FIGS. 2 to 5, the steps of the base materials 21 and 22 are previously provided on the base material before hot pressing. However, the adhesive resin layer 11 may be stacked between the base materials 21 and 22 and hot pressed. One or both of the base materials 21 and 22 are deformed to cause a step. For example, when irregularities are provided on the pressing surfaces 31a, 32a of the molds 31, 32, the flexible substrates 21, 22 such as a resin film can be deformed. Since the adhesive resin layer 11 initially has fluidity, it can follow the steps of the base materials 21 and 22. In addition, by performing thermal polymerization between hot presses, the adhesive resin layer 11 is hardened, and generation of voids and bubbles can be suppressed. Furthermore, by bonding the base materials 21 and 22 to the adhesive layer 25, the deformation of the base material is fixed, and irregularities can be formed. When the convex portion is formed on the inner surface of the base material, the concave portion may be formed on the outer surface on the back side.

為了提升接著性樹脂層11的操作性，接著性樹脂層11係以藉由於100~250℃的溫度及30秒~10分鐘的時間加熱來進行熱硬化為佳。熱硬化以至少一部分的條件在上述溫度及時間範圍的下進行為佳，以能夠在全範圍的條件熱硬化為較佳。實際使用時的熱硬化條件，亦可以是上述範圍外。但是，從保存性的觀點而言，以在常溫係實質上不進行熱硬化為佳，例如在100℃以下的溫度，具有加熱10分鐘以內不會熱硬化的性質為佳。 In order to improve the operability of the adhesive resin layer 11, the adhesive resin layer 11 is preferably thermally cured by heating at a temperature of 100 to 250°C and a time of 30 seconds to 10 minutes. The thermal curing is preferably carried out under at least a part of the conditions within the above-mentioned temperature and time range, and is preferably capable of thermal curing under a full range of conditions. The thermal curing conditions during actual use may be outside the above range. However, from the viewpoint of storability, it is preferable that the thermosetting is not substantially performed at room temperature. For example, at a temperature of 100° C. or lower, it is preferable to have the property of not being thermosetting within 10 minutes of heating.

在接著性樹脂層11未硬化的狀態(加熱前)，在溫度23℃之儲存彈性模數係以1×104~1×106Pa為佳。又，接著性樹脂層11藉由加熱而熱硬化之後，在溫度23℃之儲存彈性模數係以1×104~1×109Pa為佳。相較於加熱前在溫度23℃之儲存彈性模數，藉由加熱而熱硬化之後，在溫度23℃之儲存彈性模 數係以變為較高為佳。該等儲存彈性模數，係各自使溫度成為23℃而能夠測定未硬化的狀態(加熱前)之接著性樹脂層、及藉由加熱而熱硬化之後的接著性樹脂層(熱硬化後的接著層)。測定儲存彈性模數時之振動頻率，係例如1Hz。測定熱硬化後的接著層之儲存彈性模數時，係不將接著性樹脂層貼合在基材，而是藉由使接著性樹脂層在隔離膜之間加熱硬化之後，將隔離膜剝離，而能夠得到熱硬化後的接著層的單體。 In a state where the adhesive resin layer 11 is not cured (before heating), the storage elastic modulus at a temperature of 23° C. is preferably 1×10 4 to 1×10 6 Pa. Furthermore, after the adhesive resin layer 11 is thermally hardened by heating, the storage elastic modulus at a temperature of 23° C. is preferably 1×10 4 to 1×10 9 Pa. Compared with the storage elastic modulus at a temperature of 23° C. before heating, it is better to have a higher storage elastic modulus at a temperature of 23° C. after heat curing by heating. These storage elastic modulus are each an adhesive resin layer capable of measuring an uncured state (before heating) at a temperature of 23°C, and an adhesive resin layer after heat curing by heating (adhesion after thermal curing) Floor). The vibration frequency when measuring the storage elastic modulus is, for example, 1 Hz. When measuring the storage elastic modulus of the thermally cured adhesive layer, the adhesive resin layer is not bonded to the base material, but the adhesive resin layer is heated and hardened between the isolation films, and then the isolation film is peeled off. In addition, the monomer of the adhesive layer after thermal curing can be obtained.

接著，更詳細地說明亦是轉移膠帶之接著性樹脂層。 Next, the adhesive resin layer which is also a transfer tape will be described in more detail.

在製造本發明的接著性樹脂層所使用之接著劑原材料組成物，由於溶解於有機溶劑者係能夠厚度精確度更良好地塗佈，因此以含有有機溶劑為佳。藉由從接著劑原材料組成物將溶劑乾燥，而能夠得到接著性樹脂層。亦即，接著劑原材料組成物的組成，係可以是在構成接著性樹脂層之接著性樹脂組成物的組成添加有溶劑者。接著性樹脂層係在常溫(熱硬化前)，能夠作為黏著劑層之功能。 The adhesive raw material composition used in the production of the adhesive resin layer of the present invention is preferably soluble in an organic solvent because it can be applied with better thickness accuracy. Therefore, it is preferable to contain an organic solvent. By drying the solvent from the adhesive raw material composition, an adhesive resin layer can be obtained. That is, the composition of the adhesive raw material composition may be one in which a solvent is added to the composition of the adhesive resin composition constituting the adhesive resin layer. The adhesive resin layer is at normal temperature (before thermal curing) and can function as an adhesive layer.

構成(A)丙烯酸系聚合物之單體，可舉出具有酯基(-COO-)之丙烯酸系單體、具有羧基(-COOH)之丙烯酸系單體、具有醯胺基(-CONR2，R係氫原子或烷基等的取代基)之丙烯酸系單體、具有腈基(-CN)之丙烯酸系單體、烯烴類、苯乙烯、乙烯酯類、乙烯醚類、乙烯基矽烷等的非丙烯酸系單體。(A)丙烯酸系聚合物係以由2種以上的單體所構成之共聚物為佳。在光聚合前之(A)丙烯酸系聚合物的數量平均分子量，例如以50,000~1,000,000左右為佳。黏度係可舉例如1,000~10,000mPa ．s左右。 The monomer constituting the (A) acrylic polymer includes acrylic monomers having an ester group (-COO-), acrylic monomers having a carboxyl group (-COOH), and having an amide group (-CONR 2 , (R substituents such as hydrogen atoms or alkyl groups) acrylic monomers, acrylic monomers having a nitrile group (-CN), olefins, styrenes, vinyl esters, vinyl ethers, vinyl silanes, etc. Non-acrylic monomer. (A) The acrylic polymer is preferably a copolymer composed of two or more monomers. The number average molecular weight of (A) acrylic polymer before photopolymerization is preferably about 50,000 to 1,000,000, for example. The viscosity system can be exemplified by 1,000 to 10,000 mPa. s or so.

作為具有酯基(-COO-)之丙烯酸系單體，可舉出(甲基)丙烯酸烷酯、具有羥基之(甲基)丙烯酸酯、具有烷氧基或聚醚基之(甲基)丙烯酸酯、具有胺基或取代胺基之(甲基)丙烯酸酯等。又，在本說明書，所謂(甲基)丙烯酸酯，係丙烯酸酯及甲基丙烯酸酯的總稱。 Examples of the acrylic monomer having an ester group (-COO-) include alkyl (meth)acrylate, (meth)acrylate having a hydroxyl group, (meth)acrylic acid having an alkoxy group or polyether group Esters, (meth)acrylates with amine groups or substituted amine groups, etc. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

作為具有羧基(-COOH)之丙烯酸系單體，可舉出丙烯酸、甲基丙烯酸、具有羧基(-COOH)之(甲基)丙烯酸酯等。 Examples of the acrylic monomer having a carboxyl group (-COOH) include acrylic acid, methacrylic acid, and (meth)acrylate having a carboxyl group (-COOH).

作為具有醯胺基(-CONR2，R係氫原子或烷基等的取代基)之丙烯酸系單體，可舉出丙烯醯胺、甲基丙烯醯胺等。 Examples of the acrylic monomer having an amide group (-CONR 2 , R-based hydrogen atom or substituent such as an alkyl group) include acrylamide and methacrylamide.

作為具有腈基(-CN)之丙烯酸系單體，可舉出丙烯腈、甲基丙烯腈等。 Examples of the acrylic monomer having a nitrile group (-CN) include acrylonitrile and methacrylonitrile.

(A)丙烯酸系聚合物係構成單體的50重量%以上，以由丙烯酸系單體所構成為佳。特別是，構成單體的50重量%以上係以由通式CH2=CR1-COOR2(式中，R1為氫或甲基，R2係表示碳數1~14的烷基)表示之(甲基)丙烯酸烷酯的1種或2種以上所構成為佳。作為(甲基)丙烯酸烷酯的具體例，可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二酯。特別是以將烷基R2的碳數為4~12的(甲基)丙烯酸烷酯作為必須(例如50~100 莫耳%)使用為佳。 (A) 50% by weight or more of acrylic polymer-based constituent monomers, preferably composed of acrylic monomers. In particular, 50% by weight or more of the constituent monomers are represented by the general formula CH 2 =CR 1 -COOR 2 (where R 1 is hydrogen or methyl, and R 2 represents an alkyl group having 1 to 14 carbon atoms) One or more types of alkyl (meth)acrylates are preferred. Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, third butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, (meth)acrylic acid N-hexyl ester, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, Dodecyl (meth)acrylate. In particular, it is preferable to use alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group R 2 (for example, 50 to 100 mol %).

又，作為含有羥基之(甲基)丙烯酸酯，可舉例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、聚乙二醇一(甲基)丙烯酸酯、聚丙二醇一(甲基)丙烯酸酯、環己烷二甲醇一(甲基)丙烯酸酯等的1種或2種以上。 Moreover, as a (meth)acrylate containing a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-Hydroxybutyl methacrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth) ) One or more types of acrylates, cyclohexanedimethanol mono(meth)acrylate and the like.

(B)胺甲酸酯丙烯酸酯係在同一分子中具有胺甲酸酯鍵(-NH-COO-)及(甲基)丙烯醯基氧基(設作X=H或CH3，CH2=CX-COO-)之化合物。1分子中的胺甲酸酯鍵之數目可為1亦可為2以上。又，1分子中的(甲基)丙烯醯基氧基的數目可為1亦可為2以上。作為胺甲酸酯丙烯酸酯，可舉例如使具有羥基之(甲基)丙烯酸酯化合物與異氰酸酯化合物反應而得到之化合物；及使多元醇化合物與聚異氰酸酯化合物反應而得到之胺甲酸酯預聚合物、具有羥基之(甲基)丙烯酸酯化合物反應而得到之化合物等。作為多元醇化合物，可舉出聚酯多元醇、聚醚多元醇等。 (B) The urethane acrylate system has a urethane bond (-NH-COO-) and a (meth)acryloyloxy group (set as X=H or CH 3 , CH 2 = CX-COO-) compound. The number of urethane bonds in one molecule may be 1 or 2 or more. In addition, the number of (meth)acryloyloxy groups in one molecule may be 1 or 2 or more. Examples of the urethane acrylate include a compound obtained by reacting a (meth)acrylate compound having a hydroxyl group and an isocyanate compound; and a urethane prepolymer obtained by reacting a polyol compound and a polyisocyanate compound. Compounds, compounds obtained by the reaction of (meth)acrylate compounds with hydroxyl groups, etc. Examples of the polyol compound include polyester polyols and polyether polyols.

相對於(A)丙烯酸系聚合物100重量份，(B)胺甲酸酯丙烯酸酯的添加量係以2~50重量份為佳。該添加量亦能夠設為40重量份以下。 The added amount of (B) urethane acrylate is preferably 2 to 50 parts by weight relative to (A) 100 parts by weight of acrylic polymer. This addition amount can also be set to 40 parts by weight or less.

(B)胺甲酸酯丙烯酸酯係藉由使用(C)熱聚合起始劑之熱硬化而成為聚合物的一部分，而且以比聚合物更低黏度低的液體(流動體)為佳。作為(B)胺甲酸酯丙烯酸酯，亦能夠使用胺甲酸酯丙烯酸酯寡聚物等的丙烯酸酯寡聚物。(B)胺甲酸 酯丙烯酸酯所具有的聚合性官能基的數目係例如1~5。 (B) The urethane acrylate is part of the polymer by heat curing using (C) a thermal polymerization initiator, and it is preferably a liquid (fluid) with a lower viscosity and lower viscosity than the polymer. As (B) urethane acrylate, acrylate oligomer such as urethane acrylate oligomer can also be used. (B) Carbamate The number of polymerizable functional groups possessed by the ester acrylate is, for example, 1 to 5.

在本發明的接著劑原材料組成物係除了(B)胺甲酸酯丙烯酸酯以外，亦能夠添加其它(D)丙烯酸系單體。作為(D)丙烯酸系單體，可舉出與構成(A)丙烯酸系聚合物之單體同樣的單體，可舉例如(甲基)丙烯酸烷酯、含有羥基的(甲基)丙烯酸酯、丙烯醯胺等。1分子中的(甲基)丙烯醯基等的聚合性官能基的數目可為1亦可為2以上。特別是，含有具有羥基之(甲基)丙烯酸酯的單體時，具有極性之羥基變得容易分散在接著性樹脂層的全體。藉此，即便在濕度較高的(進而高溫的)環境，水分亦不容易凝聚且能夠抑制接著性樹脂層產生白濁，因此為較佳。 In addition to the (B) urethane acrylate, other (D) acrylic monomers can be added to the adhesive raw material composition of the present invention. Examples of the (D) acrylic monomer include the same monomers as the monomer constituting the (A) acrylic polymer, and examples thereof include alkyl (meth)acrylate, hydroxyl-containing (meth)acrylate, Acrylic amide and so on. The number of polymerizable functional groups such as (meth)acryloyl group in one molecule may be 1 or 2 or more. In particular, when a (meth)acrylate monomer having a hydroxyl group is included, the polar hydroxyl group is easily dispersed throughout the adhesive resin layer. Accordingly, even in an environment with high humidity (and further high temperature), moisture is not easily aggregated, and it is possible to suppress the occurrence of white turbidity in the adhesive resin layer, which is preferable.

相對於(A)丙烯酸系聚合物100重量份，(D)丙烯酸系單體的添加量，係以30重量份以下為佳。胺甲酸酯丙烯酸酯(或胺甲酸酯丙烯酸酯與丙烯酸系單體之合計)的添加量太多時，在使其熱聚合後之情況，有接著性樹脂層的接著力過分降低之情形。(B)胺甲酸酯丙烯酸酯與(D)丙烯酸系單體的合計添加量，係以2~50重量份為佳。該添加量亦能夠設為40重量份以下。 The amount of the (D) acrylic monomer added is preferably 30 parts by weight or less relative to (A) 100 parts by weight of the acrylic polymer. If the added amount of urethane acrylate (or the total of urethane acrylate and acrylic monomer) is too much, the adhesive force of the adhesive resin layer may be excessively reduced after thermal polymerization. . The total addition amount of (B) urethane acrylate and (D) acrylic monomer is preferably 2 to 50 parts by weight. This addition amount can also be set to 40 parts by weight or less.

作為(C)熱聚合起始劑，可舉出藉由熱而分解來使單體聚合(自由基聚合)及樹脂開始硬化之自由基起始劑。作為自由基起始劑，亦已知在低溫起作用之氧化還原起始劑及有機金屬化合物等，但是就接著性樹脂層的操作性而言，係以在較高溫起作用之(有機)過氧化物系、偶氮系等為佳。熱聚合起始劑係在轉移膠帶的製造過程，特別是為了在溶劑的乾燥步驟不 產生反應或(或者)半衰，熱聚合起始劑的半衰期變為1分鐘之溫度(以下有時稱為「1分鐘半衰期溫度」)，係以比接著劑原材料組成物所含有的有機溶劑之沸點更高為佳。又，為了使熱聚合起始劑在熱壓時的溫度以充分地反應一定時間，材料的1分鐘半衰期溫度以比熱壓設定溫度更低50℃以上為佳。 Examples of the (C) thermal polymerization initiator include a radical initiator that decomposes by heat to polymerize the monomer (radical polymerization) and starts to harden the resin. As free radical initiators, redox initiators and organometallic compounds that act at low temperatures are also known, but in terms of the operability of the adhesive resin layer, they are (organic) that act at higher temperatures. Oxide systems, azo systems, etc. are preferred. The thermal polymerization initiator is used in the manufacturing process of transfer tape, especially in order to avoid Reaction or (or) half-life occurs, and the half-life of the thermal polymerization initiator becomes a temperature of 1 minute (hereinafter sometimes referred to as "1 minute half-life temperature"), which is higher than the organic solvent contained in the raw material composition of the adhesive Higher boiling point is better. In addition, in order to allow the temperature of the thermal polymerization initiator to react sufficiently during hot pressing for a certain period of time, the 1 minute half-life temperature of the material is preferably 50°C or more lower than the set temperature of hot pressing.

作為(有機)過氧化物系的熱聚合起始劑之具體例，可舉出過氧化苯甲醯基、過氧化乙醯、過氧化癸醯、過氧化月桂醯等的過氧化二醯、過氧化二異丙苯、過氧化二-第三丁基等的過氧化二烷基、過氧化苯甲酸第三丁酯、第三丁基過氧化-己酸2-乙酯等的過氧化烷酯、異丙苯過氧化氫、第三丁基過氧化氫等的過氧化氫等。尤其是以上述1分鐘半衰期溫度為100℃以上之有機過氧化物為佳，以1分鐘半衰期溫度在100℃~200℃的範圍內之有機過氧化物為較佳。作為此種有機過氧化物，可舉出過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化新庚酸第三丁酯、過氧化三甲基乙酸第三己酯、過氧化三甲基乙酸第三丁酯、過氧化二月桂醯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、過氧化二琥珀酸、第三己基過氧化-己酸2-乙酯、第三丁基過氧化-己酸2-乙酯、1,1-雙(第三己基過氧化)環己烷、1,1-雙(第三丁基過氧化)環己烷、過氧化異丙基一碳酸第三己酯、第三丁基過氧化順丁烯二酸、第三丁基過氧化己酸3,5,5-三甲酯、第三丁基過氧化一碳酸異丙酯、第三丁基過氧化一碳酸2-乙基己酯、過氧化月桂酸第三丁酯、過氧化苯甲酸第三己酯、過氧化乙酸第三丁酯、過氧化苯甲酸第三丁酯、4,4-雙(第三丁基過氧化)戊酸正丁酯、過氧化二異丙苯、 過氧化二-第三己基、過氧化二-第三丁基、對薄荷烷過氧化氫等。 Specific examples of (organic) peroxide-based thermal polymerization initiators include benzoyl peroxide, acetyl peroxide, decyl peroxide, and laurel peroxide. Diperoxybenzene, di-tert-butyl peroxide, and other dialkyl peroxides, tert-butylperoxybenzoate, tert-butylperoxy-hexanoic acid 2-ethyl ester, and other alkyl peroxides , Cumene hydrogen peroxide, third butyl hydrogen peroxide and other hydrogen peroxide. In particular, the organic peroxide having a one-minute half-life temperature of 100°C or higher is preferred, and the organic peroxide having a one-minute half-life temperature in the range of 100°C to 200°C is preferred. Examples of such organic peroxides include trihexyl neodecanoate peroxide, tributyl neodecanoate peroxide, tertiary butyl neoheptanoate, and trihexyl trimethylacetate. Ester, tributyl peroxytrimethylacetate, dilauryl peroxide, 2,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, disuccinic acid peroxide, third Hexyl peroxy-hexanoic acid 2-ethyl ester, tertiary butyl peroxy-hexanoic acid 2-ethyl ester, 1,1-bis (third hexyl peroxide) cyclohexane, 1,1-bis (third butyl (Cyclohexane), cyclohexane, isopropyl peroxide, trihexyl monocarbonate, tert-butyl maleic acid peroxide, tert-butyl hexanoic acid 3,5,5-trimethyl, Tertiary butyl isopropyl peroxycarbonate, tertiary butyl 2-ethylhexyl peroxymonocarbonate, tertiary butyl laurate peroxide, tertiary hexyl peroxybenzoate, tertiary peroxyacetic acid Butyl ester, tert-butyl peroxybenzoate, 4,4-bis(tert-butylperoxy) n-butyl valerate, dicumyl peroxide, Di-t-hexyl peroxide, di-t-butyl peroxide, p-menthane hydrogen peroxide, etc.

作為偶氮系的熱聚合起始劑，可舉出2,2’-偶氮雙(異丁腈)、2,2’-偶氮雙(2-甲基丁腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(4-氰基戊腈)、2,2’-偶氮雙4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(甲基異丁酸酯)、1,1’-偶氮雙(1-環己烷腈)等。 Examples of azo-based thermal polymerization initiators include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), and 2,2'- Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-cyanovaleronitrile), 2,2'-azobis 4-methoxy-2,4- Dimethylvaleronitrile), 2,2'-azobis (methyl isobutyrate), 1,1'-azobis (1-cyclohexanenitrile), etc.

相對於(A)丙烯酸系聚合物100重量份，(C)熱聚合起始劑的添加量係以0.001~0.5重量份為佳。 The addition amount of the (C) thermal polymerization initiator is preferably 0.001 to 0.5 parts by weight relative to (A) 100 parts by weight of the acrylic polymer.

在本發明的接著性樹脂層，亦能夠添加聚合延遲劑。藉由使用聚合延遲劑，能夠容易地控制聚合度。又，從使段差追隨性提升的觀點而言，乃是較佳。 It is also possible to add a polymerization retardant to the adhesive resin layer of the present invention. By using a polymerization delay agent, the degree of polymerization can be easily controlled. Also, from the viewpoint of improving the followability of the step difference, it is preferable.

接著性樹脂組成物能夠進一步含有(A)~(C)以外的任意成分。例如為了使(A)丙烯酸系聚合物、或藉由(B)胺甲酸酯丙烯酸酯的聚合而生成的聚合物交聯，係能夠適合使用異氰酸酯系交聯劑、環氧系交聯劑、金屬鉗合物化合物等的(E)交聯劑(硬化劑)。此時，按照必要，作為(A)丙烯酸系聚合物或(B)胺甲酸酯丙烯酸酯的至少一部分，係能夠使用具有與(E)交聯劑反應的官能基之聚合物或單體。與(E)交聯劑反應之官能基，例如異氰酸酯系交聯劑時，係羥基或羧基等。相對於聚合物的官能基，(E)交聯劑的添加量係例如以1.5當量以下為佳。 The subsequent resin composition can further contain optional components other than (A) to (C). For example, in order to crosslink (A) an acrylic polymer or a polymer produced by polymerization of (B) urethane acrylate, an isocyanate crosslinking agent, an epoxy crosslinking agent, (E) Crosslinking agents (hardeners) such as metal clamp compounds. At this time, as necessary, as at least a part of the (A) acrylic polymer or (B) urethane acrylate, a polymer or monomer having a functional group that reacts with the (E) crosslinking agent can be used. The functional group that reacts with the (E) crosslinking agent is, for example, an isocyanate-based crosslinking agent, such as a hydroxyl group or a carboxyl group. The amount of the (E) crosslinking agent added is preferably 1.5 equivalents or less with respect to the functional group of the polymer.

藉由(E)交聯劑(硬化劑)之(A)丙烯酸系聚合物的硬化，亦可在貼合在被接著物前之製造接著性樹脂層之階段，藉由熟化(aging)而使其進行。 The curing of (A) acrylic polymer by (E) crosslinking agent (hardener) can also be done by aging at the stage of manufacturing an adhesive resin layer before bonding to the object Its going on.

作為其它任意成分，可舉例如抗氧化劑、填充劑、可塑劑等。在製造接著性樹脂層所使用的接著劑原材料組成物，亦可含有水或有機溶劑等的溶劑，亦可為無溶劑的漿狀組成物。在基材上存在ITO等的氧化物導電膜或卑金屬等有腐蝕的可能性之材料，且其與接著性樹脂層接觸時，作為接著性樹脂組成物的材料，係以使用削減酸等的腐蝕性成分、例如酸價低的聚合物為佳。 Examples of other optional components include antioxidants, fillers, and plasticizers. The adhesive raw material composition used for manufacturing the adhesive resin layer may contain a solvent such as water or an organic solvent, or may be a solvent-free slurry composition. When there is a material that may be corroded by an oxide conductive film such as ITO or a base metal on the substrate, and it is in contact with the adhesive resin layer, as the material of the adhesive resin composition, the use of acid reduction or the like Corrosive components such as polymers with low acid value are preferred.

本發明的接著性樹脂層的製造，以使硬化的成分亦即胺甲酸酯丙烯酸酯寡聚物成分盡可能的硬化為佳。又，丙烯酸系聚合物及胺甲酸酯丙烯酸酯寡聚物成分之分子量較大，作為塗料常產生相溶性變差之情形。因此，以添加相溶劑為佳。無反應性的相溶劑亦無妨，但是因為有在黏著劑層產生分離之可能性，所以能夠使用的材料為受到限定之可能性較高，而且依照種類或添加量而有在耐久試驗產生發泡等的問題之可能性且泛用性較低。因此，在熱反應時若存有與胺甲酸酯丙烯酸酯寡聚物成分一起硬化之相溶劑時，因為高分子化而亦能夠抑制發泡等之緣故，以選定具有反應基之材料為佳。而且使用如反應後變硬的丙烯酸系單體作為相溶劑時，在可期待塗料的安定性之同時，亦能夠期待硬化後黏著劑層變硬之效果。丙烯酸系單體，係除了相溶性良好以外，相較於丙烯酸系聚合物或胺甲酸酯丙烯酸酯寡聚物，因為黏度較低，故可在塗料的黏度太高時添加，藉以調整至在製膜時最適合的黏度，而有助於生產性提升。添加的丙烯酸系單體有時可能比胺甲酸酯丙烯酸酯寡聚物更多。 In the production of the adhesive resin layer of the present invention, it is preferable to harden the urethane acrylate oligomer component which is a hardened component as much as possible. In addition, the acrylic polymer and the urethane acrylate oligomer component have a large molecular weight, which often causes poor compatibility as a paint. Therefore, it is better to add a phase solvent. A non-reactive phase solvent is no problem, but because of the possibility of separation in the adhesive layer, the materials that can be used are more likely to be limited, and depending on the type or amount of addition, foaming may occur in the durability test The possibility of such problems and low universality. Therefore, if there is a phase solvent that hardens together with the urethane acrylate oligomer component during the thermal reaction, it is preferable to select a material having a reactive group because the polymerization can also suppress foaming and the like. . In addition, when an acrylic monomer that hardens after the reaction is used as a phase solvent, the stability of the coating can be expected, and the effect of hardening the adhesive layer after hardening can also be expected. Acrylic monomers, in addition to good compatibility, compared to acrylic polymers or urethane acrylate oligomers, because the viscosity is lower, so it can be added when the viscosity of the coating is too high, in order to adjust to The most suitable viscosity during film production, which helps to improve productivity. The added acrylic monomer may sometimes be more than the urethane acrylate oligomer.

(接著性樹脂層的製造方法) (Method for manufacturing adhesive resin layer)

在本發明之接著性樹脂層(轉移膠帶)，係能夠藉由將接著劑原材料組成物在含有溶劑的狀態下塗佈在隔離膜、乾燥，而且使用隔離膜保護而製造。接著劑原材料組成物，係以使用塑模或管刮刀而塗佈為佳。在溶劑的乾燥，係以使用乾燥機等使其乾燥為佳。關於溶劑的乾燥時間，考慮生產性時，係以10分鐘以下為佳，以2~5分鐘為更佳。又，因為必須將有機溶劑充分地乾燥，所以在有機溶劑的沸點以上之溫度使其乾燥為佳，以在熱聚合起始劑的1分鐘半衰期溫度以下進行乾燥為佳。 The adhesive resin layer (transfer tape) of the present invention can be manufactured by applying an adhesive raw material composition to a separator in a state containing a solvent, drying, and protecting it using a separator. The adhesive raw material composition is preferably applied using a mold or a tube blade. For drying the solvent, it is better to use a dryer or the like to dry it. Regarding the drying time of the solvent, when considering productivity, it is preferably 10 minutes or less, and more preferably 2 to 5 minutes. In addition, since the organic solvent must be sufficiently dried, it is preferable to dry the organic solvent at a temperature above the boiling point of the organic solvent, preferably at a temperature below the half-life temperature of 1 minute of the thermal polymerization initiator.

以上，基於較佳實施形態而說明了本發明，但是本發明係不被上述的實施形態限定，在不脫離本發明的要旨之範圍能夠進行各種改變。 The present invention has been described above based on the preferred embodiments. However, the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention.

積層體係在3片以上的基材之間，亦可各自具有接著性樹脂層。在積層體所包含之2層以上的接著性樹脂層的1層以上(較佳為全部)係以本實施形態的接著性樹脂層為佳。 The lamination system is between three or more substrates, and each may have an adhesive resin layer. One or more (preferably all) of the two or more adhesive resin layers included in the laminate are preferably the adhesive resin layers of this embodiment.

將積層體熱壓時，亦可在一對模具之間配置2個以上的積層體。該配置係沒有特別限定，可藉由模具而在壓縮方向堆積2個以上的積層體，亦可在對壓縮方向為垂直的面內(例如任一模具的按壓面上)排列2個以上的積層體。亦可使上述的夾雜物介於2個以上的積層體之間。 When the laminate is hot-pressed, two or more laminates may be arranged between a pair of dies. The arrangement is not particularly limited, and two or more laminates can be deposited in the compression direction by a mold, or two or more laminates can be arranged in a plane perpendicular to the compression direction (for example, the pressing surface of any mold) body. The above-mentioned inclusions may be interposed between two or more laminates.

在本發明，係在製造如第1圖的接著性樹脂層11之後，製造如第3圖的積層結構，而且在如第4圖的結構經過熱處理而製造如第5圖的積層體30。在第1圖的接著性樹脂層11之製造時點，係以設有從含有溶劑的接著劑原材料組成物藉 由加熱將溶劑除去之步驟為佳。又，在隨後之貼合後的製程條件，必須將接著性樹脂層11加熱而使聚合開始。 In the present invention, after the adhesive resin layer 11 shown in FIG. 1 is manufactured, the layered structure shown in FIG. 3 is manufactured, and the structure shown in FIG. 4 is subjected to heat treatment to manufacture the layered body 30 shown in FIG. 5. At the time of manufacture of the adhesive resin layer 11 in FIG. 1, the adhesive raw material composition containing the solvent is used to borrow The step of removing the solvent by heating is preferred. In addition, in the process conditions after the subsequent bonding, the adhesive resin layer 11 must be heated to start polymerization.

(加壓條件) (Pressure condition)

在本發明的加壓時，為了對積層體施加的加熱溫度成為100~250℃的熱，模具的溫度必須在比所需要的加熱溫度更高的溫度加熱。模具的溫度係以100~300℃為佳，更佳為150~300℃。在基材或基材的一部分含有聚對酞酸乙二酯，將該聚對酞酸乙二酯在例如180℃、10分鐘左右進行加熱時，對酞酸乙二酯寡聚物成分析且由於析出的成分致使外觀產生不良時，以將熱壓時的加熱溫度設為180℃以下為佳。 In the pressurization of the present invention, in order for the heating temperature applied to the laminate to be 100 to 250°C, the temperature of the mold must be higher than the required heating temperature. The temperature of the mold is preferably 100 to 300°C, more preferably 150 to 300°C. When the base material or a part of the base material contains polyethylene terephthalate, when the polyethylene terephthalate is heated at, for example, 180° C. for about 10 minutes, the phthalate oligomer is analyzed and When the precipitated components cause a poor appearance, it is preferable to set the heating temperature during hot pressing to 180° C. or lower.

在基材不含有聚對酞酸乙二酯，而使用不析出對酞酸乙二酯寡聚物成分之素材時，以設為100~300℃即可。關於本發明的加壓時間，從生產性的觀點而言，反應以在2分鐘以內結束為佳。又，有關加壓溫度．時間，可設定為可使積層體的強度變得充分的設定。 When the base material does not contain polyethylene terephthalate and a material that does not precipitate an ethylene terephthalate oligomer component is used, it may be set to 100 to 300°C. Regarding the pressurizing time of the present invention, from the viewpoint of productivity, the reaction is preferably completed within 2 minutes. Also, about the pressurization temperature. The time can be set so that the strength of the laminate becomes sufficient.

實施例 Examples

以下，基於實施例而具體地說明本發明。 Hereinafter, the present invention will be specifically described based on examples.

(實施例1) (Example 1)

使用作為含有(A)丙烯酸系聚合物之聚合物溶液之SK-Dyne(註冊商標)2094(綜研化學股份公司、酸價：33、數量平均分子量7萬、固形分濃度25%)、作為交聯劑之E-AX(綜研化學股份公司)，相對於丙烯酸系聚合物100重量份，交聯劑以0.56重量份的比例調配。在所得到的混合物，添加作為(B)胺甲酸酯丙烯酸酯之UV-3310B(日本合成化學工業股份公司、 在60℃的黏度：40000~70000mPa．s、重量平均分子量Mw：5000、寡聚物官能基數：2)20重量份、及作為(C)熱聚合起始劑之4,4-雙(第三丁基過氧化)戊酸正丁酯(日油股份公司製；製品名：PERHEXA(註冊商標)V)0.04重量份而調製接著劑原材料組成物。接著劑原材料組成物係含有乙酸乙酯(沸點77℃)作為溶劑，而改善作為用以塗佈的塗料之黏度等的性狀。 As a polymer solution containing (A) acrylic polymer, SK-Dyne (registered trademark) 2094 (Zhongyan Chemical Co., Ltd., acid value: 33, number average molecular weight 70,000, solid content concentration 25%), as cross-linking The E-AX (Zhongyan Chemical Co., Ltd.) of the agent is blended at a ratio of 0.56 parts by weight to 100 parts by weight of the acrylic polymer. To the obtained mixture, UV-3310B (Japan Synthetic Chemical Industry Co., Ltd., Viscosity at 60°C: 40000~70000mPa. s, weight average molecular weight Mw: 5000, oligomer functional group number: 2) 20 parts by weight, and (C) thermal polymerization initiator 4,4-bis (third butyl peroxy) n-butyl valerate (Manufactured by NOF Corporation; product name: PERHEXA (registered trademark) V) 0.04 parts by weight to prepare an adhesive raw material composition. The adhesive raw material composition contains ethyl acetate (boiling point 77°C) as a solvent to improve the properties such as the viscosity of the paint used for coating.

將該接著劑原材料組成物，使用塗佈器且以在乾燥後之接著劑樹脂層(黏著劑層)的厚度成為50μm之方式塗佈在隔離膜(藤森工業股份公司製；製品名：125E-0010DG2.5AS、厚度125μm)的上面後，在乾燥步驟於90℃、2分鐘的條件下使溶劑乾燥而製造積層有接著性樹脂層之積層體。 This adhesive raw material composition was applied to a separator (manufactured by Fujimori Industries Co., Ltd.) so that the thickness of the adhesive resin layer (adhesive layer) after drying became 50 μm using an applicator. 125E-0010DG2.5AS, thickness 125 μm ), the solvent was dried under the drying step at 90° C. for 2 minutes to produce a laminate with an adhesive resin layer.

其次，在得到的積層體之接著性樹脂層的上面，貼合隔離膜(藤森工業股份公司製；製品名：38E-0010BDAS、厚度38μm)而製造實施例1的接著性樹脂薄膜。 Next, on the adhesive resin layer of the obtained laminate, a separator (manufactured by Fujimori Industry Co., Ltd.; product name: 38E-0010BDAS, thickness 38 μm ) was bonded to produce an adhesive resin film of Example 1.

隨後，藉由進行1星期的熟化，使丙烯酸系聚合物與交聯劑的反應結束，而形成存在經交聯的丙烯酸系聚合物、胺甲酸酯丙烯酸酯、及熱聚合起始劑的3種類之接著性樹脂層。 Subsequently, by performing aging for one week, the reaction of the acrylic polymer and the crosslinking agent is ended, and a crosslinked acrylic polymer, a urethane acrylate, and a thermal polymerization initiator 3 are formed. Type of adhesive resin layer.

有關實施例1~13及比較例1~3，係在表1記載之接著劑原材料組成物的組成及製造條件下，進行在隔離膜之間包含接著性樹脂層之積層體的製造。 In Examples 1 to 13 and Comparative Examples 1 to 3, a laminate including an adhesive resin layer between separators was manufactured under the composition and manufacturing conditions of the adhesive raw material composition described in Table 1.

[表1]

Figure 105105824-A0202-12-0021-1
[Table 1]
Figure 105105824-A0202-12-0021-1

又，在表1，商品係以溶液的方式市售時，重量份的數值係表示構成其中接著性樹脂層之各成分的重量份。「SK-Dyne 2094」及「SK-Dyne 2147」係各自表示SK-Dyne(註冊商標)2094、SK-Dyne(註冊商標)2147。「N-7136」係表示丙 烯酸系聚合物的商品名(日本合成化學工業股份公司)。「CORONATE HX」係表示CORONATE(註冊商標)HX(日POLYURETHANE工業股份公司)。「E-AX」係表示環氧系硬化劑(綜研化學股份公司)，以及「TD-75」係表示異氰酸酯系硬化劑(綜研化學股份公司)。「UV-3310B」及「UV-1700」係表示胺甲酸酯丙烯酸酯的商品名(日本合成化學工業股份公司)。「4HBA」係表示丙烯酸4羥基丁酯。 In addition, in Table 1, when the commercial product is commercially available as a solution, the numerical value of parts by weight represents the parts by weight of each component constituting the adhesive resin layer therein. "SK-Dyne 2094" and "SK-Dyne 2147" refer to SK-Dyne (registered trademark) 2094 and SK-Dyne (registered trademark) 2147, respectively. "N-7136" means C Trade name of enoic acid-based polymer (Japan Synthetic Chemical Industry Co., Ltd.). "CORONATE HX" stands for CORONATE (registered trademark) HX (Japan Polyurethane Industrial Co., Ltd.). "E-AX" stands for epoxy-based hardener (Zhongyan Chemical Co., Ltd.), and "TD-75" stands for isocyanate-based hardener (Zhongyan Chemical Co., Ltd.). "UV-3310B" and "UV-1700" represent the trade name of urethane acrylate (Japan Synthetic Chemical Industry Co., Ltd.). "4HBA" means 4-hydroxybutyl acrylate.

「PERHEXA(註冊商標)V」係表示以4,4-雙(第三丁基過氧化)戊酸正丁酯作為有效成分之熱聚合起始劑。 「PEROCTA(註冊商標)O」係表示以1,1,3,3-四甲基丁基過氧化己酸2-乙酯作為有效成分之熱聚合起始劑。「PERBUTYL(註冊商標)O」係以第三丁基過氧化-己酸2-乙酯作為有效成分之熱聚合起始劑。「PERHEXA(註冊商標)HC」係以1,1-雙(第三己基過氧化)環己烷作為有效成分之熱聚合起始劑。「PERHEXA(註冊商標)Z」係以過氧化苯甲酸第三己酯作為有效成分之熱聚合起始劑。「Irg651」係以2,2-二甲氧基-2-苯基苯乙酮(別名苄基二甲縮酮)作為有效成分之光聚合起始劑。 "PERHEXA (registered trademark) V" is a thermal polymerization initiator that uses 4,4-bis (third butyl peroxy) valerate as the active ingredient. "PEROCTA (registered trademark) O" means a thermal polymerization initiator with 1,1,3,3-tetramethylbutylhexanoic acid 2-ethyl ester as an active ingredient. "PERBUTYL (registered trademark) O" is a thermal polymerization initiator with tert-butyl peroxy-hexanoic acid 2-ethyl ester as an active ingredient. "PERHEXA (registered trademark) HC" is a thermal polymerization initiator that uses 1,1-bis(third hexyl peroxide) cyclohexane as an active ingredient. "PERHEXA (registered trademark) Z" is a thermal polymerization initiator using tert-hexyl benzoate as an active ingredient. "Irg651" is a photopolymerization initiator with 2,2-dimethoxy-2-phenylacetophenone (alias benzyl dimethyl ketal) as an active ingredient.

<試驗結果> <test result>

其次，說明評價方法及其結果。 Next, the evaluation method and its results will be explained.

(藉由熱壓後的外觀確認之段差追隨性的評價方法) (Evaluation method of step followability by external appearance confirmation after hot pressing)

作為基材，準備1片平坦的聚對酞酸乙二酯(PET)薄膜，另準備1片在表面形成有20μm的印刷段差之聚對酞酸乙二酯(PET)薄膜。模具係可使加壓後的基材外表面(積層體的外表面) 成為平滑，模具係使用具有互相平滑的表面之模具。事先將一側的隔離膜從接著性樹脂薄膜剝離而貼合在形成有印刷段差之PET薄膜，藉由熱壓機在模具之間將該貼合薄膜與未形成有印刷段差之平滑的PET薄膜夾住且進行熱壓。目視確認熱壓後立刻貼合後的積層體(貼合品)之外觀，而且外觀係以下述的方式進行評價。 As a base material, one flat polyethylene terephthalate (PET) film was prepared, and another polyethylene terephthalate (PET) film with a printing step of 20 μm formed on the surface was prepared. The mold system allows the outer surface of the base material after pressurization (the outer surface of the laminate) To be smooth, the mold uses molds having mutually smooth surfaces. Separate one side of the separation film from the adhesive resin film in advance and attach it to the PET film with the printed step difference. Use a hot press between the mold and the smooth PET film without the printed step difference. Clamp and heat press. The appearance of the laminated body (laminated product) immediately after hot pressing was visually confirmed, and the appearance was evaluated in the following manner.

○：藉由目視無法觀察到在積層體面上有氣泡、缺陷，且外觀良好。 ○: No bubbles or defects were observed on the surface of the laminate by visual observation, and the appearance was good.

△：藉由目視能夠觀察到在積層體面上有一點點的氣泡、或缺陷，但是係實際上沒有損害的水準之外觀。 △: A slight amount of bubbles or defects on the surface of the laminate can be observed by visual observation, but it is a level appearance that is not actually damaged.

×：藉由目視能夠觀察到在積層體面上有氣泡、或缺陷，且外觀為容許範圍外。 ×: It is possible to visually observe bubbles or defects on the surface of the laminate, and the appearance is outside the allowable range.

又，段差追隨性如下述進行評價。 In addition, the step followability is evaluated as follows.

○：無法確認在印刷段差部分有氣泡。 ○: It is impossible to confirm the presence of bubbles in the printing step.

△：能夠確認在印刷段差部分有一點點的氣泡。 △: It is possible to confirm that there is a little bubble in the printing step.

×：能夠確認在印刷段差部分有氣泡。 ×: It can be confirmed that there are bubbles in the printing step.

(接著強度的評價方法) (The evaluation method of the next strength)

接著強度的評價，係基於熱壓後的積層體(貼合品)的接著強度之測定值，如下述地進行評價。將接著性樹脂薄膜的一方之隔離膜剝離，而將接著性樹脂層的一面貼合在厚度100μm的聚對酞酸乙二酯(PET)薄膜，而且將另一方的隔離膜剝離，且將黏著劑層的反面貼合在作為被接著物之厚度1mm的鹼石灰玻璃後，在23℃、50%RH環境下放置1小時放置後，以剝離速度300mm/min使其剝離，且測定其於180°的剝離強度。 The evaluation of the subsequent strength is based on the measured value of the adhesive strength of the laminate (laminated product) after hot pressing, and is evaluated as follows. The one side of the adhesive resin film is peeled off, and one side of the adhesive resin layer is bonded to a polyethylene terephthalate (PET) film with a thickness of 100 μm, and the other side of the separator is peeled off and adhered After attaching the reverse side of the agent layer to the soda lime glass with a thickness of 1 mm as the adherend, it was left at 23°C and 50% RH for 1 hour, and then peeled off at a peeling speed of 300 mm/min. ° Peel strength.

○：接著強度為20N/25mm以上。 ○: The adhesive strength is 20 N/25 mm or more.

△：接著強度為5N/25mm以上且未滿20N/25mm。 △: The strength is then 5N/25mm or more and less than 20N/25mm.

×：接著強度為未滿5N/25mm。 ×: The following strength is less than 5N/25mm.

將依照上述評價方法之結果，顯示在下述的表2。總評價係如下述地進行評價。 The results according to the above evaluation method are shown in Table 2 below. The overall evaluation system is evaluated as follows.

◎：外觀、段差追隨性及接著強度的全部為「○」。 ◎: All of appearance, step followability and adhesive strength are "○".

○：外觀、段差追隨性及接著強度的全部為「△」或「○」，至少一個為「△」，且「○」的數目比「△」的數目更多。 ○: All of appearance, step followability, and adhesive strength are “△” or “○”, at least one is “△”, and the number of “○” is more than the number of “△”.

△：外觀、段差追隨性及接著強度的全部為「△」或「○」，而且「△」的數目比「○」的數目更多。 △: All of appearance, step followability and adhesive strength are "△" or "○", and the number of "△" is more than the number of "○".

×：外觀、段差追隨性及接著強度的至少一者為「×」。 ×: At least one of appearance, step followability, and adhesive strength is “×”.

Figure 105105824-A0202-12-0024-2
Figure 105105824-A0202-12-0024-2

(熱壓後的外觀確認評價結果) (Appearance confirmation evaluation result after hot pressing)

在實施例，能夠確認係追隨印刷段差。認為這是因為除了(A)丙烯酸系聚合物以外，亦在接著劑原材料組成物添加(B)胺甲酸酯丙烯酸酯作為流動性高的成分之緣故。 In the embodiment, it can be confirmed that the system follows the printing step. This is considered to be because (B) urethane acrylate was added to the adhesive raw material composition as a highly fluid component in addition to (A) the acrylic polymer.

在比較例3，確認在印刷段差部分產生氣泡。在該例子，認為是因為由不含有(B)胺甲酸酯丙烯酸酯之接著劑原材料組成物形成接著性樹脂層，所以無法追隨藉由具有印刷段差之模具進行加壓而產生之基材的變形。 In Comparative Example 3, it was confirmed that bubbles were generated in the printing step. In this example, it is considered that because the adhesive resin layer is formed of an adhesive raw material composition that does not contain (B) urethane acrylate, it is impossible to follow the base material produced by pressurization with a mold having a printing step Deformed.

比較例1~3的情況，係從熱壓釋放時確認在全面產生發泡。認為是，在比較例1雖然含有光聚合起始劑，但是因為是藉由熱壓將不含有熱聚合起始劑之接著劑原材料組成物加熱之緣故；在比較例2雖然含有胺甲酸酯丙烯酸酯，但是因為是藉由熱壓將不含有熱聚合起始劑之接著劑原材料組成物加熱，丙烯酸系單體不容易進行聚合之緣故。 In the cases of Comparative Examples 1 to 3, it was confirmed that foaming occurred in all areas when released from hot pressing. It is considered that although Comparative Example 1 contains a photopolymerization initiator, it is because the raw material composition of the adhesive that does not contain the thermal polymerization initiator is heated by hot pressing; and Comparative Example 2 contains a carbamate Acrylic esters, but because the adhesive raw material composition containing no thermal polymerization initiator is heated by hot pressing, acrylic monomers are not easily polymerized.

比較例1的接著劑原材料組成物之處方雖然亦可藉由紫外線照射使其硬化，但是目前不可能在被不透明的模具加壓的狀態下進行照射紫外線，致使在由加壓狀態下被釋放之時點產生發泡。因此必須在熱壓中進行反應，只要是能夠實現該思想之手法，任何手法均無妨，但是認為不需要新的製造設備投資且不增加步驟，使用熱反應起始劑之方法係最有效的。 Although the adhesive raw material composition of Comparative Example 1 can be hardened by ultraviolet irradiation, it is currently impossible to irradiate ultraviolet rays under pressure from an opaque mold, resulting in release under pressure. Foaming occurs at a time. Therefore, the reaction must be carried out in hot pressing. Any method can be used as long as the idea can be realized, but it is considered that the method of using a hot reaction initiator is the most effective method without requiring investment in new manufacturing equipment and without adding steps.

在實施例，因為接著性樹脂層係在流動性高狀態被貼合在貼合有PET等的基材，所以即便微細的凹凸亦能夠堅固地密著。而且，可認為是藉由熱壓使得流動性高的單體產生流動，在追隨變形後，藉由熱而慢慢地進行熱聚合反應、單體成分進行高分子化，使得接著性樹脂層的流動性降低且以變形後的狀態硬化，所以不僅是在變形部不產生氣泡，而且亦不產生基材之間的發泡。 In the embodiment, since the adhesive resin layer is bonded to the base material to which PET or the like is bonded in a state of high fluidity, even fine irregularities can be firmly adhered. Furthermore, it can be considered that the monomer with high fluidity is caused to flow by hot pressing, and after following the deformation, the thermal polymerization reaction is slowly performed by heat, and the monomer component is polymerized to make the adhesive resin layer The fluidity is reduced and it is hardened in the deformed state, so not only does not generate bubbles in the deformed portion, but also does not cause foaming between the base materials.

實施例5、6的情況，係因為將接著劑原材料組成 物的調配品長時間放置時會產生分離，所以必須立刻使用。此外，雖然外觀及段差追隨性良好，但是因為係接近半導體加工用或搬運用黏著膠帶之調配比，所以黏著力降低且成為具有再加工性。然而，為了在耐久試驗為合格，所以可依照用途而有使用。只有在實施例1所使用的胺甲酸酯丙烯酸酯在賦予熱而使其反應且硬化時，會變得不溶解於丙烯酸系聚合物溶液，所以無法製造用以塗佈之塗料。又，以實施例1所製成之接著性樹脂薄膜在貼合前進行熱處理時，與接著劑相同地黏性會降低，產生密著性極端地變低且不密著之問題。 In the case of Examples 5 and 6, it is because the raw material of the adhesive is composed The preparation of the product will separate when it is left for a long time, so it must be used immediately. In addition, although the appearance and step followability are good, it is close to the compounding ratio of the adhesive tape for semiconductor processing or transportation, so the adhesive force is reduced and it has reworkability. However, in order to pass the endurance test, it can be used according to the application. Only when the urethane acrylate used in Example 1 is heated and reacted and hardened, it becomes insoluble in the acrylic polymer solution, so the paint for coating cannot be produced. In addition, when the adhesive resin film prepared in Example 1 was subjected to heat treatment before bonding, the viscosity was reduced as in the adhesive, resulting in a problem that the adhesiveness became extremely low and did not adhere.

如實施例13那樣地添加相溶性良好的4HBA，係具有確保塗料安定性之效果。因為丙烯酸系聚合物的分子量越大耐熱性及耐久性有變得越良好之傾向，所以盡可能使用分子量較大的聚合物為佳。 Adding 4HBA with good compatibility as in Example 13 has the effect of ensuring the stability of the paint. Since the larger the molecular weight of the acrylic polymer, the higher the heat resistance and durability, the better the molecular weight of the polymer.

相較於實施例1，實施例14係藉由添加較具有流動性之丙烯酸系單體，接著性樹脂層製膜時的調平性良好，且能夠觀察到膜厚的均勻性有提升之傾向。 Compared with Example 1, in Example 14, by adding a more fluid acrylic monomer, the leveling of the adhesive resin layer during film formation is good, and the tendency to improve the uniformity of the film thickness can be observed .

不限於上述實施例所記載的例子，將過氧化物進行各種變更而實施同樣的評價之結果，得知過氧化物的1分鐘半衰期溫度為100~200℃左右時，同樣地能夠藉由熱壓而接著。1分鐘半衰期溫度比100℃更低的情況，過氧化物在熱壓前進行分解，而有無法得到充分的接著強度而產生發泡之情形。過氧化物的1分鐘半衰期溫度太高時，因為所使用的薄膜基材會進行收縮及劣化而必須在短時間進行熱處理，致使反應未充分地進行，乃是不佳。 Not limited to the examples described in the above examples, the results of performing the same evaluation with various changes to the peroxides show that when the 1-minute half-life temperature of the peroxides is about 100 to 200°C, it can be similarly performed by hot pressing And then. When the temperature at a half-life of 1 minute is lower than 100°C, the peroxide decomposes before hot pressing, and there may be cases where sufficient adhesive strength cannot be obtained and foaming may occur. When the one-minute half-life temperature of the peroxide is too high, it is undesirable because the film substrate used shrinks and deteriorates and must be heat-treated in a short time, so that the reaction does not proceed sufficiently.

11‧‧‧接著性樹脂層 11‧‧‧adhesive resin layer

11a、11b‧‧‧接著性樹脂層的兩面(黏著面) 11a, 11b‧‧‧Two sides of adhesive resin layer (adhesive surface)

20‧‧‧積層體 20‧‧‧Layered body

21、22‧‧‧基材 21, 22‧‧‧ substrate

21a、22a‧‧‧內表面 21a, 22a‧‧‧Inner surface

21b、22b‧‧‧外表面 21b, 22b‧‧‧External surface

23‧‧‧凸部 23‧‧‧Convex

24‧‧‧段差的角落部 24‧‧‧ Corner

Claims (7)

一種接著性樹脂層，其係含有具有透明性的丙烯酸系接著性樹脂組成物之單層的接著性樹脂層，其特徵在於：前述接著性樹脂組成物至少含有(A)丙烯酸系聚合物、(B)胺甲酸酯丙烯酸酯、及(C)熱聚合起始劑，前述接著性樹脂層相對於前述(A)丙烯酸系聚合物100重量份，含有前述(B)胺甲酸酯丙烯酸酯的添加量為2~50重量份，及前述(C)熱聚合起始劑的添加量為0.001~0.07重量份，前述接著性樹脂層係於常溫在兩面具有黏著性，能夠藉由於100~250℃的溫度及加熱30秒~10分鐘的時間而熱硬化。 An adhesive resin layer comprising a single-layer adhesive resin layer having a transparent acrylic adhesive resin composition, characterized in that the adhesive resin composition contains at least (A) an acrylic polymer, ( B) A urethane acrylate, and (C) a thermal polymerization initiator, the adhesive resin layer containing the (B) urethane acrylate relative to 100 parts by weight of the (A) acrylic polymer The addition amount is 2-50 parts by weight, and the addition amount of the aforementioned (C) thermal polymerization initiator is 0.001~0.07 parts by weight. The adhesive resin layer has adhesiveness on both sides at normal temperature, which can be 100~250°C. The temperature and heating time of 30 seconds to 10 minutes and heat hardening. 如申請專利範圍第1項所述之接著性樹脂層，其中前述熱聚合起始劑為過氧化物。 The adhesive resin layer as described in item 1 of the patent application range, wherein the thermal polymerization initiator is a peroxide. 如申請專利範圍第2項所述之接著性樹脂層，其中前述過氧化物之具有1分鐘的半衰期之溫度為100℃以上。 The adhesive resin layer as described in item 2 of the patent application, wherein the temperature of the peroxide having a half-life of 1 minute is 100°C or higher. 如申請專利範圍第1或2項所述之接著性樹脂層，其中前述(A)丙烯酸系聚合物，係藉由硬化劑交聯而成之丙烯酸系聚合物。 The adhesive resin layer as described in item 1 or 2 of the patent application, wherein the aforementioned (A) acrylic polymer is an acrylic polymer cross-linked by a hardener. 如申請專利範圍第4項所述之接著性樹脂層，其中前述硬化劑，係含有異氰酸酯系化合物或環氧系化合物的至少1種類。 The adhesive resin layer as described in item 4 of the patent application range, wherein the hardener contains at least one kind of isocyanate compound or epoxy compound. 如申請專利範圍第1或2項所述之接著性樹脂層，其中前述接著性樹脂組成物，係含有前述(B)胺甲酸酯丙烯酸酯以外的(D)丙烯酸系單體。 The adhesive resin layer as described in item 1 or 2 of the patent application range, wherein the adhesive resin composition contains (D) an acrylic monomer other than the (B) urethane acrylate. 一種接著性樹脂薄膜，其特徵在於：在2片隔離膜之間，積 層如申請專利範圍第1至6項中任一項所述之接著性樹脂層而成。 An adhesive resin film, characterized in that: between two isolation films, The layer is formed by the adhesive resin layer described in any one of items 1 to 6 of the patent application.
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